Polycycloolefin polymer and inorganic nanoparticle compositions as optical materials

ABSTRACT

Embodiments in accordance with the present invention encompass compositions encompassing a latent catalyst and a thermal or photoactivator along with one or more monomers which undergo ring open metathesis polymerization (ROMP) when said composition is heated to a temperature from 50° C. to 100° C. or higher to form a substantially transparent film. Alternatively the compositions of this invention also undergo polymerization when subjected to suitable radiation. The monomers employed therein have a range of refractive index from 1.4 to 1.6 and thus these compositions can be tailored to form transparent films of varied refractive indices. The compositions of this invention further comprises inorganic nanoparticles which form transparent films and further increases the refractive indices of the compositions. Accordingly, compositions of this invention are useful in various opto-electronic applications, including as coatings, encapsulants, fillers, leveling agents, among others.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.62/543,449 filed Aug. 10, 2017, which is incorporated herein byreference in its entirety.

BACKGROUND OF THE INVENTION Field of the Invention

Embodiments in accordance with the present invention relate generally toa single component mass polymerizable polycycloolefin monomer andinorganic nanoparticle dispersed to compositions having high opticaltransparency and exhibiting suitable refractive index that match therefractive index of layers in optical devices, such as optical sensors,light emitting diodes (LEDs), organic light emitting diode (OLED), amongother devices. More specifically, this invention relates to singlecomponent room temperature stable compositions encompassing norbornene(NB) based olefinic monomers in which inorganic nanoparticles aredispersed, which undergo mass polymerization when subjected to highertemperatures or photolytic conditions to form transparent optical layershaving utility in a variety of opto-electronic applications including asencapsulants, coatings, and fillers.

Description of the Art

Organic light emitting diodes (OLEDs) are gaining importance in avariety of applications, including flat panel televisions and otherflexible displays, among other applications. However, conventionalOLEDs, particularly, bottom emitting OLEDs suffer from a drawback inthat only about half of the generated photons are emitted into the glasssubstrate out of which 25% are extracted into air. The other half of thephotons are wave-guided and dissipated in the OLED stack. This loss ofphotons is primarily attributed to the refractive index (n) mismatchbetween the organic layers (n=1.7-1.9) and the glass substrate (n=1.5).By matching the refractive index of the substrate (n=1.8) and organiclayers and augmenting the distance of the emission zone to the cathodeto suppress plasmonic losses light extraction into the substrate can beincreased to 80-90%. See, for example, G. Gaertner et al., Proc. OfSPIE, Vol. 6999, 69992T pp 1-12 (2008). In addition, OLEDs also poseother challenges; in that OLEDs being organic materials, they aregenerally sensitive to moisture, oxygen, temperature, and other harshconditions. Thus, it is imperative that OLEDs are protected from suchharsh atmospheric conditions. See for example, U. S. Patent ApplicationPublication No. US2012/0009393 A1.

In order to address some of the issues faced by the art, U.S. Pat. No.8,263,235 discloses use of a light emitting layer formed from at leastone organic light emitting material and an aliphatic compound not havingan aromatic ring, and a refractive index of the light emitting from 1.4to 1.6. The aliphatic compounds described therein are generally avariety of polyalkyl ethers, and the like, which are known to beunstable at high temperatures, see for example, Rodriguez et al., I & ECProduct Research and Development, Vol. 1, No. 3, 206-210 (1962).

The co-pending U.S. patent application Ser. No. 15/253,980, filed Sep.1, 2016, discloses a two component mass polymerizable composition whichis capable of tailoring to the desirable refractive index and issuitable as a filler and a protective coating material, thus potentiallyuseful in the fabrication of a variety of OLED devices. Although thisapproach may provide certain advantages it still suffers from thedrawback of being two component system and in addition organic polymersalone may not be able to provide required high refractive index for theOLED applications. Furthermore, there is also a need for masspolymerizable compositions which are stable at room temperatures as wellas OLED fabrication conditions and yet polymerize instantly whensubjected to suitable higher temperatures and/or photolytic conditions.

Accordingly, there is still a need for filler materials that complementthe refractive index of OLEDs and yet exhibit high transparency and goodthermal properties, among other desirable properties. In addition, it isdesirable that such organic filler materials readily form a permanentprotective coatings and are available as a single component compositionfor dispensing with such OLED layers.

Thus, it is an object of this invention to provide organic/inorganicnanoparticle composite materials that overcome the gaps faced by theart. More specifically, it is an object of this invention to provide asingle component composition that will mass polymerize under theconditions of the fabrications of an OLED device. It is further anobject of this invention to provide stable single component masspolymerizable composition with no change in viscosity at or below normalstorage conditions but which undergoes mass polymerization only underthe process conditions in which the OLED device is finally fabricated,such as for example by the use of radiation and/or thermal process.

Other objects and further scope of the applicability of the presentinvention will become apparent from the detailed description thatfollows.

SUMMARY OF THE INVENTION

Surprisingly, it has now been found that by employing a single componentfiller composition, it is now possible to fabricate an OLED devicehaving a transparent optical layer which features hitherto unachievableproperties, i.e., refractive index in the range of 1.4 to 1.8 or higher,high colorless optical transparency, desirable film thickness of thefiller layer typically in the range of 10 to 20 μM but can be tailoredto lower or higher film thickness depending upon the intendedapplication, compatible with the OLED stack, particularly the cathodelayer (a very thin layer on the top of the OLED stack), compatible withpolymerization of the formulation on the OLED stack, including fastpolymerization time and can be photolytically or thermally treated atless than 100° C., adhesion to both OLED stack and glass cover, and thelike. It is also important to note that the compositions of thisinvention are expected to exhibit good uniform leveling across the OLEDlayer which typically requires a low viscosity. Further, compositions ofthis invention are also expected to exhibit low shrinkage due to theirrigid polycycloolefinic structure. In addition, as the components ofthis invention undergo fast mass polymerization upon application they donot leave behind any fugitive small molecules which can damage the OLEDstack. Generally, no other small molecule additives need to be employedthus offering additional advantages. Most importantly, the compositionsof this invention are stable (i. e., no change in viscosity) at ambientatmospheric conditions including up to 35° C. for several hours, andundergo mass polymerization only above 50° C. or higher temperature orunder photolytic conditions. The compositions cure very quickly whensubjected to higher than 50° C. and generally the compositions are curedin less than one hour.

Advantageously, the compositions of this invention are also compatiblewith a “one drop fill” (commonly known as “ODF”). In a typical ODFprocess, which is commonly used to fabricate a top emission OLED device,a special optical fluid is applied to enhance the transmission of lightfrom the device to the top cover glass, and the fluid is dispensed by anODF method. Although the method is known as ODF which can be misleadingbecause several drops or lines of material are generally dispensedinside the seal lines. After applying the fluid, the fluid spreads outas the top glass is laminated, analogous to die-attach epoxy. Thisprocess is generally carried out under vacuum to prevent air entrapment.The present invention allows for a material of low viscosity whichreadily and uniformly coats the substrate with rapid flow in a shortperiod of time. Even more advantageously, the present inventionovercomes the deficiencies faced by the prior art in that a singlecomponent composition is much more convenient than employing a twocomponent system especially in an ODF method.

Accordingly, there is provided a single component compositionencompassing:

a) one or more monomers of formula (I):

wherein:

-   -   m is an integer 0, 1 or 2;    -   R₁, R₂, R₃ and R₄ are the same or different and each        independently selected from the group consisting of hydrogen,        halogen, methyl, ethyl, linear or branched (C₃-C₁₆)alkyl,        perfluoro(C₁-C₁₂)alkyl, hydroxy(C₁-C₁₆)alkyl,        (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl,        (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₀)aryl,        perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkyl, tri(C₁-C₆)alkoxysilyl and a        group of formula (A):

—Z-Aryl  (A)

wherein:

-   -   Z is a bond or a group selected from the group consisting of:        -   (CR₅R₆)_(a), O(CR₅R₆)_(a), (CR₅R₆)_(a)O,            (CR₅R₆)_(a)—O—(CR₅R₆)_(b), (CR₅R₆)_(a)—O—(SiR₅R₆)_(b),            (CR₅R₆)_(a)—(CO)O—(CR₅R₆)_(b),            (CR₅R₆)_(a)—O(CO)—(CR₅R₆)_(b), (CR₅R₆)_(a)—(CO)—(CR₅R₆)_(b),            where a and b are integers which may be the same or            different and each independently is 1 to 12;        -   R₅ and R₆ are the same or different and each independently            selected from the group consisting of hydrogen, methyl            ethyl, linear or branched (C₃-C₆)alkyl, hydroxy, methoxy,            ethoxy, linear or branched (C₃-C₆)alkyloxy, acetoxy,            (C₂-C₆)acyl, hydroxymethyl, hydroxyethyl, linear or branched            hydroxy(C₃-C₆)alkyl, phenyl and phenoxy;    -   Aryl is phenyl or phenyl substituted with one or more of groups        selected from the group consisting of methyl, ethyl, linear or        branched (C₃-C₆)alkyl, hydroxy, methoxy, ethoxy, linear or        branched (C₃-C₆)alkyloxy, acetoxy, (C₂-C₆)acyl, hydroxymethyl,        hydroxyethyl, linear or branched hydroxy(C₃-C₆)alkyl, phenyl and        phenoxy;    -   b) a latent organo-transition metal catalyst comprising a metal        selected from the group consisting of ruthenium and osmium; and    -   c) one or more additives selected from the group consisting of a        photoactive acid generator, a photoactive base generator, a        thermal acid generator, a thermal base generator and a mixture        in any combination thereof; and wherein        said monomer of formula (I) is having a refractive index of at        least 1.5 and said composition is in a clear liquid form at room        temperature.

In another aspect of this invention there is further provided acomposition comprising one or more monomers of formula (I) as describedherein along with a latent organo-transition metal catalyst as describedherein and a dispersion comprising nanoparticles.

In another aspect of this invention there is also provided a kitencompassing the composition of this invention for forming a transparentfilm.

DETAILED DESCRIPTION

The terms as used herein have the following meanings:

As used herein, the articles “a,” “an,” and “the” include pluralreferents unless otherwise expressly and unequivocally limited to onereferent.

Since all numbers, values and/or expressions referring to quantities ofingredients, reaction conditions, etc., used herein and in the claimsappended hereto, are subject to the various uncertainties of measurementencountered in obtaining such values, unless otherwise indicated, allare to be understood as modified in all instances by the term “about.”

Where a numerical range is disclosed herein such range is continuous,inclusive of both the minimum and maximum values of the range as well asevery value between such minimum and maximum values. Still further,where a range refers to integers, every integer between the minimum andmaximum values of such range is included. In addition, where multipleranges are provided to describe a feature or characteristic, such rangescan be combined. That is to say that, unless otherwise indicated, allranges disclosed herein are to be understood to encompass any and allsub-ranges subsumed therein. For example, a stated range of from “1 to10” should be considered to include any and all sub-ranges between theminimum value of 1 and the maximum value of 10. Exemplary sub-ranges ofthe range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8,and 5.5 to 10, etc.

As used herein, the symbol “

” denotes a position at which the bonding takes place with anotherrepeat unit or another atom or molecule or group or moiety asappropriate with the structure of the group as shown.

As used herein, “hydrocarbyl” refers to a group that contains carbon andhydrogen atoms, non-limiting examples being alkyl, cycloalkyl, aryl,aralkyl, alkaryl, and alkenyl. The term “halohydrocarbyl” refers to ahydrocarbyl group where at least one hydrogen has been replaced by ahalogen. The term perhalocarbyl refers to a hydrocarbyl group where allhydrogens have been replaced by a halogen.

As used herein, the expression “(C₁-C₆)alkyl” includes methyl and ethylgroups, and straight-chained or branched propyl, butyl, pentyl and hexylgroups. Particular alkyl groups are methyl, ethyl, n-propyl, isopropyland tert-butyl. Derived expressions such as “(C₁-C₄)alkoxy”,“(C₁-C₄)thioalkyl”, “(C₁-C₄)alkoxy(C₁-C₄)alkyl”, “hydroxy(C₁-C₄)alkyl”,“(C₁-C₄)alkylcarbonyl”, “(C₁-C₄)alkoxycarbonyl(C₁-C₄)alkyl”,“(C₁-C₄)alkoxycarbonyl”, “diphenyl(C₁-C₄)alkyl”, “phenyl(C₁-C₄)alkyl”,“phenylcarboxy(C₁-C₄)alkyl” and “phenoxy(C₁-C₄)alkyl” are to beconstrued accordingly.

As used herein, the expression “cycloalkyl” includes all of the knowncyclic groups. Representative examples of “cycloalkyl” includes withoutany limitation cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, and the like. Derived expressions such as“cycloalkoxy”, “cycloalkylalkyl”, “cycloalkylaryl”, “cycloalkylcarbonyl”are to be construed accordingly.

As used herein, the expression “(C₁-C₆)perfluoroalkyl” means that all ofthe hydrogen atoms in said alkyl group are replaced with fluorine atoms.Illustrative examples include trifluoromethyl and pentafluoroethyl, andstraight-chained or branched heptafluoropropyl, nonafluorobutyl,undecafluoropentyl and tridecafluorohexyl groups. Derived expression,“(C₁-C₆)perfluoroalkoxy”, is to be construed accordingly. It shouldfurther be noted that certain of the alkyl groups as described herein,such as for example, “(C₁-C₆)alkyl” may partially be fluorinated, thatis, only portions of the hydrogen atoms in said alkyl group are replacedwith fluorine atoms and shall be construed accordingly.

As used herein, the expression “(C₆-C₁₀)aryl” means substituted orunsubstituted phenyl or naphthyl. Specific examples of substitutedphenyl or naphthyl include o-, p-, m-tolyl, 1,2-, 1,3-, 1,4-xylyl,1-methylnaphthyl, 2-methylnaphthyl, etc. “Substituted phenyl” or“substituted naphthyl” also include any of the possible substituents asfurther defined herein or one known in the art.

As used herein, the expression “(C₆-C₁₀)aryl(C₁-C₄)alkyl” means that the(C₆-C₁₀)aryl as defined herein is further attached to (C₁-C₄)alkyl asdefined herein. Representative examples include benzyl, phenylethyl,2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl and the like.

“Halogen” or “halo” means chloro, fluoro, bromo, and iodo.

In a broad sense, the term “substituted” is contemplated to include allpermissible substituents of organic compounds. In a few of the specificembodiments as disclosed herein, the term “substituted” meanssubstituted with one or more substituents independently selected fromthe group consisting of (C₁-C₆)alkyl, (C₂-C₆)alkenyl,(C₁-C₆)perfluoroalkyl, phenyl, hydroxy, —CO₂H, an ester, an amide,(C₁-C₆)alkoxy, (C₁-C₆)thioalkyl and (C₁-C₆)perfluoroalkoxy. However, anyof the other suitable substituents known to one skilled in the art canalso be used in these embodiments.

It should be noted that any atom with unsatisfied valences in the text,schemes, examples and tables herein is assumed to have the appropriatenumber of hydrogen atom(s) to satisfy such valences.

By the term “latent organo-transition metal catalyst” is meantorgano-transition metal compounds that show little or no catalyticactivity at a particular (usually ambient atmospheric conditions)temperature and initiate such activity either upon heat or light orboth.

By the term “derived” is meant that the polymeric repeating units arepolymerized (formed) from, for example, polycyclic norbornene-typemonomers in accordance with formulae (I) or (IV) wherein the resultingpolymers are ring opened metathesis polymerized (ROMP), for example, the2,3 double bond of norbornene-type monomers are ring opened andpolymerized as shown below:

Accordingly, in accordance with the practice of this invention there isprovided a single component composition encompassing

-   -   a) one or more monomers of formula (I):

wherein:

-   -   m is an integer 0, 1 or 2;    -   R₁, R₂, R₃ and R₄ are the same or different and each        independently selected from the group consisting of hydrogen,        halogen, methyl, ethyl, linear or branched (C₃-C₁₆)alkyl,        perfluoro(C₁-C₂₁)alkyl, hydroxy(C₁-C₁₆)alkyl,        (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl,        (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₀)aryl,        perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkyl, tri(C₁-C₆)alkoxysilyl and a        group of formula (A):

—Z-Aryl  (A)

wherein:

-   -   Z is a bond or a group selected from the group consisting of:        -   (CR₅R₆)_(a), O(CR₅R₆)_(a), (CR₅R₆)_(a)O,            (CR₅R₆)_(a)—O—(CR₅R₆)_(b), (CR₅R₆)_(a)—O—(SiR₅R₆)_(b),            (CR₅R₆)_(a)—(CO)O—(CR₅R₆)_(b),            (CR₅R₆)_(a)—O(CO)—(CR₅R₆)_(b), (CR₅R₆)_(a)—(CO)—(CR₅R₆)_(b),            where a and b are integers which may be the same or            different and each independently is 1 to 12;        -   R₅ and R₆ are the same or different and each independently            selected from the group consisting of hydrogen, methyl,            ethyl, linear or branched (C₃-C₆)alkyl, hydroxy, methoxy,            ethoxy, linear or branched (C₃-C₆)alkyloxy, acetoxy,            (C₂-C₆)acyl, hydroxymethyl, hydroxyethyl, linear or branched            hydroxy(C₃-C₆)alkyl, phenyl and phenoxy;    -   Aryl is phenyl or phenyl substituted with one or more of groups        selected from the group consisting of methyl, ethyl, linear or        branched (C₃-C₆)alkyl, hydroxy, methoxy, ethoxy, linear or        branched (C₃-C₆)alkyloxy, acetoxy, (C₂-C₆)acyl, hydroxymethyl,        hydroxyethyl, linear or branched hydroxy(C₃-C₆)alkyl, phenyl and        phenoxy;    -   b) a latent organo-transition metal catalyst comprising a metal        selected from the group consisting of ruthenium and osmium; and    -   c) one or more additives selected from the group consisting of a        photoactive acid generator, a photoactive base generator, a        thermal acid generator, a thermal base generator and a mixture        in any combination thereof.

As used herein the Aryl may further include the following:

substituted or unsubstituted biphenyl of formula:

substituted or unsubstituted naphthyl of formula:

substituted or unsubstituted terphenyl of formula:

substituted or unsubstituted anthracenyl of formula:

substituted or unsubstituted fluorenyl of formula:

where R_(x) in each occurrence is independently selected from methyl,ethyl, linear or branched (C₃-C₁₂)alkyl or (C₆-C₁₀)aryl.

As noted, the monomer of formula (I) is having a refractive index of atleast 1.5. The composition is in a clear liquid form at roomtemperature.

The monomers employed in the composition of this invention arethemselves known in the literature or can be prepared by any of theknown methods in the art to make such or similar types of monomers.

In addition, the monomers as described herein readily undergo masspolymerization, i.e., in their neat form without use of any solventswhen polymerized under mass ring open metathesis polymerization (ROMP)conditions using certain transition metal catalysts, such as forexample, organo-ruthenium and organo-osmium compounds. See for example,R. H. Grubbs et al., Handbook of Metathesis, Ed.: Wiley-VCH, Weinheim,Germany, 2003, R. H. Grubbs et al., Acc. Chem. Res. 2001, 34, 18-29, R.H. Grubbs et al., Angew. Chem. Int. Ed., 2006, 45, 3760-3765. Also, seeU.S. Pat. No. 6,838,489, pertinent portions of which are incorporatedherein by reference. The term “mass polymerization” as used herein shallhave the generally accepted meaning in the art. That is, apolymerization reaction that is generally carried out substantially inthe absence of a solvent. In some cases, however, a small proportion ofsolvent is present in the reaction medium. For example, such smallamounts of solvent may be used to dissolve the latent catalyst and/orthe activator or convey the same to the reaction medium. Also, somesolvent may be used to reduce the viscosity of the monomer. The amountof solvent that can be used in the reaction medium may be in the rangeof 0 to 5 weight percent based on the total weight of the monomersemployed. Any of the suitable solvents that dissolves the catalyst,activator and/or monomers can be employed in this invention. Examples ofsuch solvents include alkanes, cycloalkane, toluene, THF,dichloromethane, dichloroethane, and the like.

Advantageously, it has now been found that one or more of the monomersthemselves can be used to dissolve the latent catalyst as well as theactivator and thus avoiding the need for the use of solvents. Inaddition, one monomer can itself serve as a solvent for the othermonomer and thus eliminating the need for an additional solvent. Forexample, if first monomer of formula (I) is a solid at room temperature,then the second monomer of formula (I), which is liquid at roomtemperature can be used as a solvent for the first monomer of formula(I) which is a solid or vice versa. Therefore, in such situations morethan one monomer can be employed in the composition of this invention.

Accordingly, it has now been surprisingly found that monomers of formula(I) serve as high refractive index materials imparting high refractiveindex to the resulting polymeric film upon mass polymerization at atemperature and/or condition different from the application of thecomposition onto a desirable substrate. In general, the monomers offormula (I) which are suitable in this invention feature a refractiveindex of at least 1.5. In some embodiments the refractive index of themonomers of formula (I) is higher than 1.5. In some other embodimentsthe refractive index of the monomers of formula (I) is in the range fromabout 1.5 to 1.6. In yet some other embodiments the refractive index ofthe monomers of formula (I) is higher than 1.55, higher than 1.6 orhigher than 1.65. In some other embodiments it may even be higher than1.7.

In general, the composition of this invention exhibits low viscosity,which can be below 100 centipoise or higher. In some embodiments, theviscosity of the composition of this invention is less than 90centipoise. In some other embodiments the viscosity of the compositionof this invention is in the range from about 10 to 100 centipoise. Inyet some other embodiments the viscosity of the composition of thisinvention is lower than 80 cP, lower than 60 cP, lower than 40 cP, lowerthan 20 cP. In some other embodiments it may even be lower than 20 cP.

When the composition of this invention contains two or more monomers,for example, they can be present in any desirable amounts that wouldbring about intended benefit, including either refractive indexmodification or viscosity modification or both. Accordingly, the molarratio of first monomer of formula (I) to second monomer of formula (II)can be from 1:99 to 99:1. In some embodiments, the molar ratio of firstmonomer of formula (I): second monomer of formula (I) is in the rangefrom 5:95 to 95:5; in some other embodiments it is from 10:90 to 90:10;it is from 20:80 to 80:20; it is from 30:70 to 70:30; it is from 60:40to 40:60; and it is 50:50, and so on. Similarly, when more than twodifferent monomers of formula (I) are employed, any ratios of suchmonomers can be used that would bring about the intended result.

In general, the compositions in accordance with the present inventionencompass the above described one or more of the monomer of formula (I)and if needed additional monomers of formula (I) distinct from eachother, as it will be seen below, various composition embodiments areselected to provide properties to such embodiments that are appropriateand desirable for the use for which such embodiments are directed, thussuch embodiments are tailorable to a variety of specific applications.

For example, as already discussed above, proper combination ofdistinctive monomers to of formula (I) makes it possible to tailor acomposition having the desirable refractive index, viscosity and opticaltransmission properties. In addition, as described further herein it maybe desirable to include other polymeric or monomeric materials, such asfor example inorganic nanoparticles which are compatible to providedesirable optical properties depending upon the end use application.Accordingly, the compositions of this invention can also include otherhigh refractive polymeric materials and/or nanoparticles which willbring about such intended benefit. Examples of such polymers includewithout any limitation, poly(α-methylstyrene), poly(vinyl-toluene),copolymers of α-methylstyrene and vinyl-toluene, and the like. Examplesof nanoparticles are described further in detail below.

Advantageously, it has further been found that the compositions of thisinvention can also contain additional monomers. In some embodiments, thecomposition according to this invention may further contain one or moremonomers selected from monomer of formula (IV).

The monomer of formula (IV) is:

wherein:

o is an integer from 0 to 2, inclusive;

D is SiR₂₁R₂₂R₂₃ or a group selected from:

—(CH₂)_(c)—O—SiR₂₁R₂₂R₂₃  (E);

—(CH₂)_(c)—SiR₂₁R₂₂R₂₃  (F); and

—(SiR₂₁R₂₂)_(c)—O—SiR₂₁R₂₂R₂₃  (G);

-   -   wherein

c is an integer from 1 to 10, inclusive, and where one or more of CH₂ isoptionally substituted with (C₁-C₁₀)alkyl, (C₁-C₁₀)perfluoroalkyl or(C₆-C₁₄)aryl;

R₁₈, R₁₉ and R₂₀ are the same or different and independently of eachother selected from hydrogen, halogen and hydrocarbyl, where hydrocarbylis selected from methyl, ethyl, linear or branched (C₃-C₁₂)alkyl,(C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl,(C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl, (C₁-C₁₂)alkoxy,(C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy,(C₆-C₁₀)aryloxy(C₁-C₃)alkyl or (C₆-C₁₀)aryloxy; and

R₂₁, R₂₂ and R₂₃ are each independently of one another methyl, ethyl,linear or branched (C₃-C₉)alkyl, substituted or unsubstituted(C₆-C₁₄)aryl, methoxy, ethoxy, linear or branched (C₃-C₉)alkoxy orsubstituted or unsubstituted (C₆-C₁₄)aryloxy.

In this aspect of the invention, it has now been found that monomers offormula (IV) provides further advantages. Namely, the monomers offormula (IV) depending upon the nature of the monomer may impart high orlow refractive index to the composition, thus it can be tailored to meetthe need. In addition, the monomers of formula (IV) generally improvethe adhesion properties and thus can be used as “adhesion modifiers.”Finally, the monomers of formula (IV) may exhibit low viscosity and goodsolubility for the latent catalyst and/or activator, among various otheradvantages.

Accordingly, any of the monomers within the scope of monomer of formula(I) can be employed in the composition of the invention. Representativeexamples of monomer of formula (I) include the following without anylimitations:

-   -   5-(4-phenylbutyl)bicyclo[2.2.1]hept-2-ene;

-   -   5-(3-phenylpropyl)bicyclo[2.2.1]hept-2-ene;

-   -   5-phenethylbicyclo[2.2.1]hept-2-ene (PENB);

-   -   5-(benzyloxy)bicyclo[2.2.1]hept-2-ene;

-   -   5-octylbicyclo[2.2.1]hept-2-ene (OctNB);

-   -   5-decylbicyclo[2.2.1]hept-2-ene (DecNB);

-   -   4,4′-(bicyclo[2.2.1]hept-5-en-2-ylmethylene)bis(2,6-di-tert-butylphenol)        (AOAONB);

-   -   bicyclo[2.2.1]hept-5-en-2-ylmethyl        3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate (AONB);

-   -   5-norbornenylmethyleugenyl acetate (EuAcNB);

-   -   5-norbornenylmethyleugenol (EuOHNB);

-   -   (bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)diphenylsilane        (NBCH₂OSiMePh₂);

-   -   (bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(ethyl)diphenylsilane;

-   -   (bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(ethyl)(methyl)(phenyl)silane;

-   -   (bicyclo[2.2.1]hept-5-en-2-ylmethoxy)dimethyl(phenyl)silane;

-   -   bicyclo[2.2.1]hept-5-en-2-yltrimethoxysilane (TMSNB);

-   -   bicyclo[2.2.1]hept-5-en-2-yltriethoxysilane (NBSi(OC₂H₅)₃);

-   -   bicyclo[2.2.1]hept-5-en-2-yl(tert-butoxy)dimethoxysilane;

-   -   (2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)trimethoxysilane;

-   -   5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene (NB(MeOH)₂); and

-   -   bicyclo[2.2.1]hept-5-en-2-yl-phenyl acetate (PhAcNB);

-   -   bicyclo[2.2.1]hept-5-en-2-yl-phenol (NBPhOH); and

-   -   5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene        (NBEtOPhPh).

In a further embodiment of this invention, the composition contains anyof the latent catalyst that would bring about the mass polymerization asdescribed herein under ROMP conditions. Generally, such suitable latentcatalysts include a number of known organo-transition metal complexes,such as organo-ruthenium or organo-osmium compounds, among others.

Accordingly, the composition of this invention encompasses a latentcatalyst which is an organo-ruthenium compound selected from the groupconsisting of a compound of formula (II) and a compound of formula(III):

and

-   -   wherein:    -   X is a halogen selected from the group consisting of chlorine,        bromine and iodine;    -   Y is selected from the group consisting of O and S;    -   Y′ is OR₉SR₉ and —N═CHC(O)O(C₁-C₆)alkyl, where R₉ is selected        from the group consisting of methyl, ethyl, linear or branched        (C₁-C₆)alkyl, (C₆-C₁₀)aryl, methoxy, ethoxy, linear or branched        (C₁-C₆)alkoxy, (C₆-C₁₀)aryloxy, —OCH(CH₃)C(O)N(CH₃)(OCH₃);    -   L is PR₃ or O═PR₃, where R is independently selected from the        group consisting of isopropyl, sec-butyl, tert-butyl,        cyclohexyl, bicyclo(C₅-C₁₀)alkyl, phenyl, benzyl, isopropoxy,        sec-butoxy, tert-butoxy, cyclohexyloxy, phenoxy and benzyloxy;    -   R₇ is selected from the group consisting of isopropyl,        sec-butyl, tert-butyl, substituted or unsubstituted cyclohexyl,        substituted or unsubstituted phenyl, substituted or        unsubstituted biphenyl and substituted or unsubstituted        naphthyl;    -   R₈ is selected from the group consisting of methyl, ethyl,        linear or branched (C₁-C₆)alkyl, (C₆-C₁₀)aryl, methoxy, ethoxy,        linear or branched (C₁-C₆)alkoxy, (C₆-C₁₀)aryloxy,        —NHCO(C₁-C₆)alkyl, —NHCO-perfluoro(C₁-C₆)alkyl,        —SO₂N((C₁-C₆)alkyl)₂ and —NO₂;    -   Ar₁, Ar₂ Ar₃ and Ar₄ are the same or different and each        independently selected from the group consisting of substituted        or unsubstituted phenyl, substituted or unsubstituted biphenyl        and substituted or unsubstituted naphthyl;

wherein said substituents are selected from the group consisting ofmethyl, ethyl, iso-propyl, tert-butyl and phenyl.

Generally, any of the latent organo-transition metal catalyst that wouldbring about ring open metathesis polymerization of the monomers offormula (I) can be employed in the composition of this invention. Morespecifically, organo-ruthenium or organo-osmium compounds that showlittle or no activity at ambient temperatures can be employed. That is,the latent catalysts that are stable at or near room temperature aremore suitable in the composition of this invention. The latent catalystsmay be activated by a variety of conditions, including without anylimitation thermal, acid, light and chemical activation. The chemicalactivation may include use of thermal acid generator or photo acidgenerators.

Another approach of rendering ROMP catalyst dormant is by deactivatingthe catalyst by addition of suitable deactivating agent, such as forexample, photo base generator. The catalyst is reactivated again by theuse of thermal acid generator or photo acid generator. Another approachin tuning the latency of a ROMP catalyst is by way of manipulating theN-heterocyclic carbene (NHC) ligand as further exemplified below.Accordingly, various different techniques as described herein can beemployed to render the catalyst latent which can be activated latereither photolytically or by thermal treatment or by chemical activationso as to facilitate fabrication of electronic devices as describedherein.

Several of the latent catalysts that are suitable to be employed in thecompositions of this invention are known in the literature or can bereadily made by any of the known procedures in the art. See for example,Grubbs, et al., Organometallics, 2011, 30 (24): 6713-6717; Sutar et al.,Angew. Chem. Int. Ed. 2016, 55, 764-767; Leitgeh, et al., Monatsh Chem(2014) 145:1513-1517; van Hensbergen, et al., J. Mater. Chem. C. 2015,3, 693-702; Grubbs, et al., J. Am. Chem. Soc., 2009, 131, 203802039;Zak, et al., Eur. J. Inorg. Chem., 2014, 1131-1136; Gawin, et al., ACSCatal. 2017, 7, 5443-5449. Further examples of such catalysts can alsobe found in U.S. Pat. No. 9,328,132, pertinent portions of which areincorporated herein by reference. Accordingly, a few of the exemplarylatent catalysts, which are organo-ruthenium compounds, without anylimitation maybe selected from the group consisting of:

-   -   1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)(tricyclohexylphosphine)-(2-oxobenzylidene)ruthenium(VI)        chloride;

-   -   where X=halogen, —OR_(a), —O(CO)R_(a)—OSO₂R_(a), where R_(a) is        (C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₄)aryl, see, for        example, U.S. Pat. No. 9,328,132, for example when X═I,        1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)(tricyclohexylphosphine)-(2-oxobenzylidene)ruthenium(VI)        iodide;

-   -   where X is Cl or I and R₁₀ is hydrogen, NO₂ or Cl;

-   -   bis-[1-(2,6-diethylphenyl)-3-phenyl-3-methyl-5,5′-dimethyl-2-imidazolidinylidene]dichloro(3-phenyl-1H-inden-1-ylidene)        ruthenium;

-   -   cis-[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-phenyl-1H-inden-1-ylidene)(triisopropylphosphite)ruthenium(II),        commercially available from Umicore.

As noted, the composition of this invention further contains one or moreadditives selected from the group consisting of a photoactive acidgenerator, a photoactive base generator, a thermal acid generator, athermal base generator and a mixture in any combination thereof.Surprisingly it has now been found that certain of the known photoactiveor thermally active compounds, such as for example, photoacid generatorsor photobase generators can be used for this purpose.

In some embodiments the photoacid generator of the formula (V) isemployed in the composition of this invention:

Aryl₁-Hal^(⊕)-Aryl₂An^(⊖)  (V)

Wherein Aryl₁ and Aryl₂ are the same or different and are independentlyselected from the group consisting of substituted or unsubstitutedphenyl, biphenyl and naphthyl; Hal is iodine or bromine; and An^(⊖) is aweakly coordinating anion (WCA) which is weakly coordinated to thecation complex. More specifically, the WCA anion functions as astabilizing anion to the cation complex. The WCA anion is relativelyinert in that it is non-oxidative, non-reducing, and non-nucleophilic.In general, the WCA can be selected from borates, phosphates, arsenates,antimonates, aluminates, boratobenzene anions, carborane, halocarboraneanions, sulfonamidate and sulfonates.

Representative examples of the compounds of formula (V) may be listed asfollows:

Wherein R₃₀ and R₃₁ are the same or different and independently of eachother selected from methyl, ethyl, linear or branched (C₃-C₁₂)alkyl,(C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl,(C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl, (C₁-C₁₂)alkoxy,(C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy,(C₆-C₁₀)aryloxy(C₁-C₃)alkyl and (C₆-C₁₀)-aryloxy. It should further benoted that more than one R₃₀ and R₃₁ substituent can be present inaforementioned compounds of formula (V1), (V2) or (V3).

Similarly, various known sulfonium salts and quaternary ammonium saltscan also be employed. Various thermal base generators as well asphotobase generators can also be employed. Representative examples ofsuch thermal base generators can be found in U.S. Pat. No. 9,690,196,pertinent portions of which are incorporated herein by reference.Representative examples of photobase generators can be found in U. S.Patent Application Publication No. US-2016-0238932-A1, pertinentportions of which are incorporated herein by reference.

Non-limiting examples of suitable additives that may be employed in thecomposition of this invention are listed below:

-   -   methyl 4-(1-methyl)octahydropyrrolo[1,2-a]pyrimidine benzoate,        commercially available as CGI 1293 from BASF;

-   -   1-(1-phenylethyl)octahydropyrrolo[l,2-a]pyrimidine, commercially        available as CGI 90 from BASF;

-   -   (4-thiophenyl)phenyl-diphenylsulfonium hexafluorophosphate; and

-   -   bis-(triphenylsulfonium) sulfide bis-hexafluorophosphate        (collectively TS-HFP);

-   -   tris(4-tert-butylphenyl)sulfonium perfluoro-1-butanesulfonate        (TTBPS-PFBS);

-   -   tris(4-tert-butylphenyl)sulfonium triflate (TTBPS-TF);

-   -   triphenylsulfonium chloride (TSP-Cl);

-   -   (4-phenoxyphenyl)diphenylsulfonium triflate (PPDP-ST);

-   -   bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate        (BTBI-PFBS);

-   -   bis(4-tert-butylphenyl)iodonium p-toluenesulfonate (BTBI-PTS);

-   -   bis(4-tert-butylphenyl)iodonium triflate (BTBPI-TF);

-   -   tolylcumyliodonium-tetrakis pentafluorophenylborate,        commercially available as Rhodorsil 2074P;

-   -   diphenyliodonium chloride (DPI-Cl);

-   -   diphenyleneiodonium chloride (DPEI-Cl);

-   -   N-hydroxy-5-norbornene-2,3-dicarboximide        perfluoro-1-butanesulfonate (HNPCI-PFBS).

Another representative class of thermal acid generators is a variety ofquaternary ammonium salts, including halides, acetates,trifluoroacetates, phosphates, hexafluorophosphates,hexafuoroantimonates and sulfonate salts. For example, sulfonate saltsmay be generically represented by the following formula:

-   -   wherein R₁₁, R₁₂, R₁₃ and R₁₄ are the same or different and each        independently selected from the group consisting of methyl,        ethyl, linear or branched (C₃-C₁₆)alkyl, perfluoro(C₁-C₁₂)alkyl,        substituted or unsubstituted (C₆-C₁₀)aryl, substituted or        unsubstituted (C₆-C₁₀)aryl(C₃-C₁₆)alkyl, (C₃-C₁₂)cycloalkyl or        wherein any two of R₁₁, R₁₂, R₁₃ and R₁₄ taken together with the        nitrogen atom to which they are attached form a (C₃-C₁₂)cyclic        or (C₅-C₁₂)bicyclic ring; and    -   R₁₅ is selected from the group consisting of methyl, ethyl,        linear or branched (C₃-C₁₆)alkyl, perfluoro(C₁-C₁₂)alkyl,        substituted or unsubstituted (C₆-C₁₀)aryl and substituted or        unsubstituted (C₆-C₁₀)aryl(C₃-C₁₆)alkyl.

Non-limiting examples of such quaternary ammonium salts include withoutany limitation tetra-alkylammonium salts, such as for example,tetraethyl ammonium acetate, tetrabutylammonium chloride, and the like.Other representative quaternary ammonium salts include a variety ofsulfonate salts commercially available under the tradename K-PURE®quaternary ammonium blocked acids, from King Industries. Variousquaternary ammonium sulfonate salts can be employed including the saltsof dinonylnaphthalene disulfonic acid, dinonylnaphthalene sulfonic acid,para-toluene sulfonic acid, dodecylbenzene sulfonic acid, methanesulfonic acid, trifluoromethane sulfonic acid and perfluorobutanesulfonic acid. Representative examples of such quaternary ammoniumsulfonates include without any limitation N,N,N-trimethyl-N-benzyltriflate, N-benzyl-N,N-dimethyl-4-nitro-N-phenyl nonafluorobutanesulfonate, 4-methyl-N-benzyl-N,N-dimethyl-N-phenyl triflate,N-benzyl-N,N-dimethyl-N-phenyl triflate,4-methoxy-N-benzyl-N,N-dimethyl-N-phenyl triflate, and the like. A fewof these quaternary ammonium salts are available commercially, forexample, TAG-2678, TAG-2689 and TAG-2700, all from King Industries.

Another class of quaternary salts includes various pyridinium sulfonatesalts of the formula shown below. Such pyridinium salts may also includeother anions such as the ones mentioned above, i.e., halides, acetates,trifluoroacetates, phosphates, hexafluorophosphates,hexafuoroantimonates and the like.

-   -   wherein n is an integer from 0 to 5;    -   R₁₅ is as defined above;    -   R₁₆ selected from the group consisting of methyl, ethyl, linear        or branched (C₃-C₁₆)alkyl, perfluoro(C₁-C₁₂)alkyl and        substituted or unsubstituted (C₆-C₁₀)aryl and substituted or        unsubstituted (C₆-C₁₀)aryl(C₃-C₁₆)alkyl; and    -   R₁₇ is independently selected from the group consisting of        methyl, ethyl, linear or branched (C₃-C₁₆)alkyl,        perfluoro(C₁-C₁₂)alkyl, substituted or unsubstituted        (C₆-C₁₀)aryl and substituted or unsubstituted        (C₆-C₁₀)aryl(C₃-C₁₆)alkyl.

Representative examples of such pyridinium salts include without anylimitation pyridinium triflate, 1-(4-methoxyphenyl)methyl-pyridiniumtriflate, and the like.

However, any of the other known photoactive or thermally activecompounds which generate the activator for the latent catalysts employedherein can also be used in the composition of this invention. All suchcompounds are part of this invention.

In another aspect of this invention there is further provided acomposition as described herein which includes a dispersion ofnanoparticles. In this aspect of the invention it has now beensurprisingly found that there is no need to add any of the additives asdescribed hereinabove. That is in this aspect of the invention thecomposition encompasses one or more monomer of formula (I), theorgano-transition compound such as organo-ruthenium compound asdescribed herein and a dispersion of nanoparticles. This compositionwhen subjected to higher temperature, such as for example from about 50°C. to about 100° C. or higher undergoes mass ring open-metathesispolymerization (ROMP) to form a transparent film.

Any of the nanoparticles known in the literature that would bring aboutsuch a change can be used in this aspect of the invention. For example,U.S. Pat. No. 8,592,511 discloses certain nanoparticles that aresuitable for this aspect of the invention, pertinent portion of which isincorporated herein by reference. Accordingly, such nanoparticlesinclude without any limitation at least one of hafnium oxide, zirconiumoxide, titanium oxide, hafnium-zirconium oxide and titanium-zirconiumoxide.

In some embodiments of this invention it has now been found that variouszirconium oxide nanoparticles are suitable to form the composition ofthis invention which readily forms transparent films as disclosedherein.

As noted, surprisingly, it has now been found that employing a suitableadditive which is either photoactive or thermally active initiator cantrigger the mass polymerization of the monomers when the composition issubjected to either an elevated temperature or to a suitable radiation.As further noted any of the photoactive or thermally active compoundsthat can bring about such an effect can be employed in the compositionof this invention.

In some embodiments of this invention the composition of this inventionmay additionally contain a photosensitizer compound which can activatethe organo-transition compound in order to facilitate the masspolymerization of the monomers of formula (I). For this purpose, anysuitable sensitizer compound can be employed in the compositions of thepresent invention. Such suitable sensitizer compounds include,photosensitizers, such as, anthracenes, phenanthrenes, chrysenes,benzpyrenes, fluoranthenes, rubrenes, pyrenes, xanthones, indanthrenes,thioxanthen-9-ones, and mixtures thereof. In some exemplary embodiments,suitable sensitizer components include 2-isopropyl-9H-thioxanthen-9-one,4-isopropyl-9H-thioxanthen-9-one, 1-chloro-4-propoxythioxanthone(commercially sold under the name CPTX from Lambson), phenothiazine, Joand mixtures thereof. Generally, photosensitizers absorb energy from theradiated light source and transfers that energy to the desirablesubstrate/reactant, which in the present invention is the photoactiveinitiator employed in the composition of this invention.

Any amount of latent catalyst and the additive initiator can be employedin the composition of this invention which will bring about the intendedresult. Generally, the molar ratio of monomer:latent catalyst:additiveis in the range of 10,000:1:1 to 5,000:1:1 or lower. In some otherembodiments such monomer:latent catalyst:photo or thermal activeinitiator is 15,000:1:1, 20,000:1:1 or higher. Again, as noted, whennanoparticles are employed then there may not be a need to use any otheradditives to activate the latent catalyst.

Advantageously, it has further been found that the composition accordingto this invention forms a substantially transparent film when masspolymerized, generally, at a temperature from 50° C. to 100° C. orhigher, for example, 150° C. or 200° C. and so on. That is to say, thatwhen the composition of this invention is heated to certain elevatedtemperature, the monomers undergo mass polymerization to form filmswhich are substantially transparent to visible light. That is, most ofthe visible light is transmitted through the film. In some embodimentssuch film formed from the composition of this invention exhibits atransmission of equal to or higher than 90 percent of the visible light.In some other embodiments such film formed from the composition of thisinvention exhibits a transmission of equal to or higher than 95 percentof the visible light. It should be further noted that any temperaturethat is suitable to carry out this mass polymerization can be employed,such as for example, 50° C. to 100° C. as indicated above. However, anytemperature below 50° C. or higher than 100° C. can also be employed. Insome embodiments the temperature employed to 60° C., 70° C., 80° C., 90°C. or higher than 120° C.

In some other embodiments the composition of this invention undergoesmass polymerization when exposed to suitable UV irradiation to form asubstantially transparent film.

In yet other embodiments the composition of this invention undergoesmass polymerization when exposed to suitable UV irradiation at atemperature from 50° C. to 100° C. to form a substantially transparentfilm.

In another embodiment of this invention, the composition of thisinvention encompasses 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB),5-norbornenylmethyl-eugenol,1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)(tricyclohexylphosphine)-(2-oxobenzylidene)ruthenium(VI)iodide and a mixture of (4-thiophenyl)phenyl-diphenylsulfoniumhexafluorophosphate and bis-(triphenylsulfonium) sulfidebis-hexafluorophosphate.

In another embodiment of this invention, the composition of thisinvention encompasses 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB),1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)(tricyclohexylphosphine)-(2-oxobenzylidene)ruthenium(VI)iodide and N,N,N-trimethyl-N-benzyl triflate.

In yet another embodiment of this invention, the composition of thisinvention encompasses 5-norbornenylmethyl-eugenol,1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro-(phenylmethylidene)(tricyclohexylphosphine)rutheniumand zirconium oxide nanoparticles.

In another embodiment of this invention, the composition of thisinvention encompasses 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB),1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)(tricyclohexylphosphine)-(2-oxobenzylidene)ruthenium(VI)chloride and a mixture of (4-thiophenyl)phenyl-diphenylsulfoniumhexafluorophosphate and bis-(triphenylsulfonium) sulfidebis-hexafluorophosphate.

In a further aspect of this invention there is provided a kit forforming a substantially transparent film. There is dispensed in this kita composition of this invention. Accordingly, in some embodiments thereis provided a kit in which there is dispensed one or more monomers offormula (I) and optionally one or more additives as described herein oroptionally a dispersion of nanoparticles so as to obtain a desirableresult and/or for intended purpose. Further, said kit comprises a latentcatalyst as described herein. The monomers of formulae (I) are the onesas described hereinabove.

In some embodiments, the aforementioned kit encompasses two or moremonomers of formula (I) distinct from one another as describedhereinabove. In some other embodiments the kit of this inventionencompasses at least two monomers wherein first monomer facilitatesdissolution of the second monomer and/or the latent catalyst and theadditives as described hereinabove. Any of the monomers of formula (I)as described herein can be used in this embodiment. The molar ratio offirst and the second monomer of formula (I) contained in thesecomponents can vary and may range from 1:99 to 99:1, or 10:90 to 90:10,20:80 to 80:20, 30:70 to 70:30, 60:40 to 40:60 or 50:50, and so on. Insome other embodiments the kit may encompass a composition whereindispensed more than two monomers of formula (I), each distinct from oneanother. Further, as noted the first monomer of formula (I) iscompletely soluble in the second monomer of formula (I) to form a clearsolution at room temperature. In some embodiments the monomer mixturemay become a clear solution at slightly elevated temperature, such asfor example, 30° C. or 40° C. or 50° C., before they undergo masspolymerization. In another aspect of this embodiment of this inventionthe composition of this invention undergoes mass polymerization at atemperature of from 50° C. to 100° C. for a sufficient length of time toform a polymeric film. That is to say that the composition of thisinvention is poured onto a surface or onto a substrate which needs to beencapsulated, and heated to a temperature of 50° C. to 100° C. in orderfor the monomers to undergo polymerization to form a solid transparentpolymer which could be in the form of a transparent film. Generally, asalready noted above, such polymerization can take place at 50° C., 60°C., 70° C., 80° C., 90° C., 100° C. or higher. The heating can also becarried out in stages to trigger the polymerization, for example to 60°C. for 5 minutes, and then heating to 70° C. for 15 minutes and so on.By practice of this invention it is now possible to obtain polymericfilms on such substrates which are substantially transparent film. The“substantially transparent film” as used herein means that the filmsformed from the composition of this invention are optically clear in thevisible light. Accordingly, in some embodiments of this invention suchfilms are having at least 90 percent of visible light transmission, insome other embodiments the films formed from the composition of thisinvention exhibit at least 95 percent of visible light transmission.

In some embodiments, the kit as described herein encompasses acomposition, which contains 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB),5-norbomenylmethyl-eugenol,1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)(tricyclohexylphosphine)-(2-oxobenzylidene)ruthenium(VI)iodide and a mixture of (4-thiophenyl)phenyl-diphenylsulfoniumhexafluorophosphate and bis-(triphenylsulfonium) sulfidebis-hexafluorophosphate.

In some other embodiments, the kit as described herein encompasses acomposition, which contains 5-norbornenylmethyl-eugenol,1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro-(phenylmethylidene)(tricyclohexylphosphine)rutheniumand zirconium oxide nanoparticles.

In another aspect of this invention there is further provided acomposition comprising one or more monomers of formula (I), a latentcatalyst, one or more additives which are a thermal or photoactive acidor base generators as described hereinabove. Any of the monomers offormula (I) as described hereinabove can be used in this aspect of theinvention. The monomers of formula (I) featuring a refractive index ofat least 1.5 and viscosity below 100 centipoise. When more than twomonomers of formula (I) are employed the first monomer is completelymiscible with the second monomer and forms a clear solution. When thecomposition is heated to a temperature in the range of from 50° C. to100° C. and optionally exposed to suitable irradiation forms asubstantially transparent film having a transmission higher than 90percent to of the visible light.

In yet another aspect of this invention there is further provided amethod of forming a substantially transparent film for the fabricationof a variety of optoelectronic device comprising:

forming a homogeneous clear composition comprising one or more monomersof formula (I), a latent catalyst and an additive selected from thermalor photoactive acid or base generator;

coating a suitable substrate with the composition or pouring thecomposition onto a suitable substrate to form a film; and

heating the film to a suitable temperature to cause polymerization ofthe monomers.

The coating of the desired substrate to form a film with the compositionof this invention can be performed by any of the coating procedures asdescribed herein and/or known to one skilled in the art, such as by spincoating. Other suitable coating methods include without any limitationspraying, doctor blading, meniscus coating, ink jet coating and slotcoating. The mixture can also be poured onto a substrate to form a film.Suitable substrate includes any appropriate substrate as is, or may beused for electrical, electronic or optoelectronic devices, for example,a semiconductor substrate, a ceramic substrate, a glass substrate.

Next, the coated substrate is baked, i.e., heated to facilitate the masspolymerization, for example to a temperature from 50° C. to 100° C. forabout 1 to 60 minutes, although other appropriate temperatures and timescan be used. In some embodiments the substrate is baked at a temperatureof from about 60° C. to about 90° C. for 2 minutes to 10 minutes. Insome other embodiments the substrate is baked at a temperature of fromabout 60° C. to about 90° C. for 5 minutes to 20 minutes.

The films thus formed are then evaluated for their optical propertiesusing any of the methods known in the art. For example, the refractiveindex of the film across the visible spectrum can be measured byellipsometry. The optical quality of the film can be determined byvisual observation. Quantitatively the percent transparency can bemeasured by visible spectroscopy. Generally, the films formed accordingto this invention exhibit excellent optical transparent properties andcan be tailored to desirable refractive index as described herein.

Accordingly, in some of the embodiments of this invention there is alsoprovided a optically transparent film obtained by the masspolymerization of the composition as described herein. In anotherembodiment there is also provided an optoelectronic device comprisingthe transparent film of this invention as described herein.

The following examples are detailed descriptions of methods ofpreparation and use of certain compounds/monomers, polymers andcompositions of the present invention. The detailed preparations fallwithin the scope of, and serve to exemplify, the more generallydescribed methods of preparation set forth above. The examples arepresented for illustrative purposes only, and are not intended as arestriction on the scope of the invention. As used in the examples andthroughout the specification the ratio of monomer to catalyst is basedon a mole to mole basis.

EXAMPLES

The following abbreviations have been used hereinbefore and hereafter indescribing some of the compounds, instruments and/or methods employed toillustrate certain of the embodiments of this invention:

PENB—5-phenethylbicyclo[2.2.1]hept-2-ene; Ru-I,1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)(tricyclohexylphosphine)-(2-oxobenzylidene)ruthenium(VI)chloride;Ru-II—1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)(tricyclohexylphosphine)-(2-oxobenzylidene)ruthenium(VI)iodide;Ru-III—bis-[1-(2,6-diethylphenyl)-3-phenyl-3-methyl-5,5′-dimethyl-2-imidazolidinylidene]dichloro(3-phenyl-1H-inden-1-ylidene)ruthenium;Ru-IV—cis-[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-phenyl-1H-inden-1-ylidene)(triisopropylphosphite)ruthenium(II);CGI 1293—methyl 4-(1-methyl)octahydropyrrolo[1,2-a]pyrimidine benzoate;CGI 90—1-(1-phenylethyl)octahydropyrrolo[1,2-a]pyrimidine;TAG-2678—thermal acid generator from King Industries; TS-HFP—a mixtureof (4-thiophenyl)phenyl-diphenylsulfonium hexafluorophosphate andbis-(triphenylsulfonium) sulfide bis-hexafluorophosphate;DPI-Cl—diphenyliodonium chloride; DPEI-Cl—diphenyleneiodonium chloride;PAG—photoacid generator; TAG—thermal acid generator.

Various monomers as used herein are either commercially available or canbe readily prepared following the procedures as described in theco-pending U.S. patent application Ser. No. 15/253,980, filed Sep. 1,2016.

The following Examples demonstrate that the compositions of thisinvention are quite stable at 35° C. for several days and can veryreadily be mass polymerized by heating to a temperature as specifiedbelow.

Example 1 Mass Polymerization of PENB

In a glass bottle, Ru-I (0.0021 g, 0.0025 mmol) was dissolved in PENB (5g, 25.21 mmol) without solvent to form a clear solution, the monomer tocatalyst ratio was at 10,000:1. To this solution was then added asolution of CGI 1293 (0.004 g 0.0075 mmol in 0.38 g acetone). Thesolution was UV light exposed (5 J/cm², broad band, 5 mins). Thesolution was free flowing even after 6 days at room temperature. To thiswas then added dilute HCl in acetone (HCl to CGI 1293 molar ratio was at3:1). The solution gelled immediately. This clearly demonstrate thatRu-I can be made dormant with a base (i.e., CGI 1293) and then activatedby addition of HCl.

Example 2 Mass Polymerization of PENB

The procedure of Example 1 was substantially repeated in Example 2,except for employing CGI 90 as the photobase to stabilize Ru-I. Theclear solution thus obtained was again free flowing even after 6 days atroom temperature and gelled immediately after addition of dilute HCl inacetone (HCl to CGI 1293 molar ratio was at 3:1).

Example 3 Mass Polymerization of PENB with Ru-II

The procedure of Example 1 was substantially repeated in Example 3,except for employing Ru-II as the catalyst and TS-HFP (0.007 g) was usedas photo acid generator. The solution was stable and free flowing withno increase in viscosity for at least two hours. The solution was UVlight exposed (5 J/cm², broad band, 5 minutes) and was heated to 100° C.for 1 hour at which time it gelled.

Examples 4-5

The procedures of Example 3 were substantially repeated in theseExamples 4 and 5 except that different PAGs as listed in Table 1 wereemployed. The PAG solution was prepared by dissolving PAG in 0.5 gethanol in Example 4 and no solvent was used in Example 5. The PAG tocatalyst ratio was at 1:1. The mixtures with PAG were UV light exposed(5 J/cm², broad band 5 minutes). All reaction mixtures were heated at100° C. for 1 hour. The results are summarized in Table 1.

TABLE 1 Example UV exposure Heating at No. PAG Solvent (1 J/cm²) 100° C.for 1 h 4 DPI-Cl ethanol Liquid Solid 5 DPEI-Cl none Liquid Solid

Example 6

In a glass bottle was placed Ru-IV (0.0022 g, 0.0025 mmol) dissolved in0.05 g anhydrous toluene. The catalyst solution was mixed with PENB (5g, 25.21 mmol). The monomer to catalyst ratio was at 10000:1. To thissolution was added triethyl phosphite (0.001 g). The triethyl phosphiteto catalyst mole ratio was at 2:1. The solution viscosity did not changefor 2 days at 30° C. The reaction mixture was heated to 100° C. andgelled after 15 min.

Example 7 Mass Polymerization of PENB/EuOHNB/Nanoparticles

In a glass bottle were placed PENB (2.5 g, 12.61 mmol), EuOHNB (2.5 g,10.86 mmol) and zirconia (ZrO₂) nanoparticle (smaller than 20 nm,Pixelligent) 50 wt. % dispersion in ethyl acetate (10 g). The solventwas stripped off using a rotary evaporator at 60° C. (10 torr) to give aclear Transparent solution. The refractive index of the solution wasmeasured using Abbe refractometer (Atago), and was 1.61 (the refractiveindex of monomer mixture alone was 1.56). To this was then injected asolution of1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexyl-phosphine)ruthenium(0.00415 g, 0.005 mmol in 0.05 g anhydrous toluene) using a syringe. Themonomer to catalyst ratio was kept at 5000:1. The composition was heatedfor 1 hour at 100° C. The inorganic residue of cured samples wasmeasured by dynamic TGA at 600° C. in air and was determined to be 38wt. %.

Example 8 Preparation of a Thin (500 nm) Nanocomposite Film

The composition of Example 8 was diluted with toluene and spin coated ata spin speed of 2000 rpm for 30 seconds on a 2-inch silicon wafer. Thefilm was heated at 120° C. on a hot plate for 5 minutes to obtain a filmthickness of around 500 nm. The refractive index of cured film wasmeasured using Ellipsometry at 589 nm and was 1.65.

Examples 9-18 Mass Polymerization of Norbornene Monomers/ZrO₂Nanoparticles

The procedures of Examples 7 and 8 were substantially repeated in theseExamples 9 to 18 except that various different monomers and ZrO₂nanoparticles as listed in Table 2 were employed.

The monomer used in each of these Examples 9 to 18, the type ofnanoparticles used (all from Pixelligent), nanoparticles loading, therefractive index of solution and films, and the loading levels of ZrO₂in the film as measured by the residue percentage from dynamic TGA ofthe resulting nanocomposites are summarized in Table 2.

TABLE 2 Monomer Polymer film Example (g, mmol) NanoparticlesNanoparticles Solution RI (residue, No. (RI) (Type) loading, wt. % RI %)9 EuOHNB ZrO₂ 50 — — (5, 21.7) (PCN-50-ETA) 10 AOAONB ZrO₂ 50 — — (5,9.7) (PCPG-2-50-ETA) 11 PENB/EuOHNB, ZrO₂ 50 1.61 1.65 (38) 50/50 moleratio (PCPG-2-50-ETA) (2.5/2.5, 12.6/10.9) (1.56) 12 PENB/EuOHNB, ZrO₂75 1.65 1.71 (67) 50/50 mole ratio (PCPG-2-50-ETA) (2.5/2.5, 12.6/10.9)(1.56) 13 PENB/EuOHNB, ZrO₂ 50 1.6 1.64 (48) 75/25 mole ratio(PCPG-2-50-ETA) (3.75/1.25, 18.9/5.4) (1.54) 14 PENB/EuOHNB, ZrO₂ 751.67 1.71 (58) 75/25 mole ratio (PCPG-2-50-ETA) (3.75/1.25, 18.9/5.4)(1.54) 15 PENB/EuOHNB, ZrO₂ 50 1.61 1.65 (42) 50/50 mole ratio(PCPB-2-50-ETA) (2.5/2.5, 12.6/10.9) (1.56) 16 PENB/EuOHNB, ZrO₂ 50 1.61.65 (44) 75/25 mole ratio (PCPB-2-50-ETA) (3.75/1.25, 18.9/5.4) (1.54)17 PENB/EuOHNB, ZrO₂ 50 1.6 1.66 (42) 50/50 mole ratio (PCPN-50-ETA)(2.5/2.5, 12.6/10.9) (1.56) 18 PENB/EuOHNB, ZrO₂ 50 1.6 1.65 (39) 75/25mole ratio (PCPN-50-ETA) (3.75/1.25, 18.9/5.4) (1.54) RI—refractiveindex

Example 19 PENB Film with Ru-III

Ru-III as described herein was dissolved in PENB (5 g, 25.21 mmol). Themonomer to catalyst ratio was 10000:1. The solution was dispensed on a5-inch bare silicon wafer with 100 μm glass bead spacers and coveredwith a second wafer. The stack was heated at 100° C. for 1 hour in anoven. After cooling, the film was removed from the wafers in water anddried at room temperature and its mechanical properties were measuredand are summarized in Table 3.

Examples 20-21 Mechanical Properties of PENB and PENB/EuOHNB/ZrO₂Nanoparticles Films

PENB/EuOHNB (50/50 weight ratio) (5 g, 23.47 mmol) were dissolved inZrO₂ nanoparticles (PCPB-2-50-ETA, Pixelligent) solution in ethylacetate (10 g). The solvent was removed using a rotary evaporator at 60°C. (10 torr). To this composition was added the respective rutheniumcatalyst as listed in Table 3 to form a clear solution. The monomer tocatalyst molar ratio was kept at 10000:1. The compositions weredispensed on a 5-inch bare silicon wafer with 100 μm glass bead spacersand covered with a second wafer. The stack was cured at 100° C. for 1hour in an oven. The films were removed from the wafers in water anddried at room temperature. Mechanical properties of the tested films aresummarized in Table 3.

TABLE 3 Example Nanoparticles Young's Tensile No. Monomer loading, wt. %Catalyst modulus, GPa ETB, % Stress, MPa 19 PENB — Ru-III 1.6 270 29 20PENB/EuOH 50 Ru-III 1.8 98 40 NB, 50/50 21 PENB/EuOH 50 Ru-II 2 80 36NB, 50/50 ETB—elongation to break

Comparative Example 1

In a glass bottle, Ru-I (0.0021 g, 0.0025 mmol) was dissolved in PENB (5g, 25.21 mmol) without solvent to form a clear solution, the monomer tocatalyst molar ratio was at 10,000:1. The solution gelled at roomtemperature in about 2 hours.

Comparative Example 2

In a glass bottle was placed Ru-IV (0.0022 g, 0.0025 mmol) dissolved in0.05 g anhydrous toluene. The catalyst solution was mixed with PENB (5g, 25.21 mmol). The monomer to catalyst ratio was at 10000:1. Thesolution gelled at 30° C. after 24 hours.

Comparative Example 3

In a glass bottle was placed Ru-IV (0.0022 g, 0.0025 mmol) dissolved in0.05 g anhydrous toluene. The catalyst solution was mixed with PENB (5g, 25.21 mmol). The monomer to catalyst ratio was at 10000:1. Thereaction mixture was heated to 100° C. it gelled after 10 min.

Comparative Example 4

In a glass bottle Ru-II (0.0022 g, 0.0025 mmol) was dissolved in PENB (5g, 25.21 mmol). The monomer to catalyst ratio was at 10000:1. Thesolution was free flowing at room temperature and was then heated to100° C. for 1 hour, the solution was still free flowing indicating thatthe catalyst was still inactive under these conditions.

Comparative Example 5

In a glass bottle Ru-II (0.0022 g, 0.0025 mmol) was dissolved in amixture of PENB (2.5 g, 12.6 mmol)/EuOHNB (2.5 g, 10.9 mmol). Themonomer to catalyst ratio was at 10000:1. The solution was free flowingat room temperature and was then heated to 100° C. for 1 hour, thesolution was still free flowing indicating that the catalyst was stillinactive under these conditions.

Although the invention has been illustrated by certain of the precedingexamples, it is not to be construed as being limited thereby; butrather, the invention encompasses the generic area as hereinbeforedisclosed. Various modifications and embodiments can be made withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A composition comprising: a) one or more monomersof formula (I):

wherein: m is an integer 0, 1 or 2; R₁, R₂, R₃ and R₄ are the same ordifferent and each independently selected from the group consisting ofhydrogen, halogen, methyl, ethyl, linear or branched (C₃-C₁₆)alkyl,perfluoro(C₁-C₁₂)alkyl, hydroxy(C₁-C₁₆)alkyl, (C₃-C₁₂)cycloalkyl,(C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl,(C₆-C₁₀)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₀)aryl,perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkyl, tri(C₁-C₆)alkoxysilyl and a group offormula (A):—Z-Aryl  (A) wherein: Z is a bond or a group selected from the groupconsisting of: (CR₅R₆)_(a), O(CR₅R₆)_(a), (CR₅R₆)_(a)O,(CR₅R₆)_(a)—O—(CR₅R₆)_(b), (CR₅R₆)_(a)—O—(SiR₅R₆)_(b),(CR₅R₆)_(a)—(CO)O—(CR₅R₆)_(b), (CR₅R₆)_(a)—O(CO)—(CR₅R₆)_(b),(CR₅R₆)_(a)—(CO)—(CR₅R₆)_(b), where a and b are integers which may bethe same or different and each independently is 1 to 12; R₅ and R₆ arethe same or different and each independently selected from the groupconsisting of hydrogen, methyl ethyl, linear or branched (C₃-C₆)alkyl,hydroxy, methoxy, ethoxy, linear or branched (C₃-C₆)alkyloxy, acetoxy,(C₂-C₆)acyl, hydroxymethyl, hydroxyethyl, linear or branchedhydroxy(C₃-C₆)alkyl, phenyl and phenoxy; Aryl is phenyl or phenylsubstituted with one or more of groups selected from the groupconsisting of methyl, ethyl, linear or branched (C₃-C₆)alkyl, hydroxy,methoxy, ethoxy, linear or branched (C₃-C₆)alkyloxy, acetoxy,(C₂-C₆)acyl, hydroxymethyl, hydroxyethyl, linear or branchedhydroxy(C₃-C₆)alkyl, phenyl and phenoxy; b) a latent organo-transitionmetal catalyst comprising a metal selected from the group consisting ofruthenium and osmium; and c) one or more additives selected from thegroup consisting of a photoactive acid generator, a photoactive basegenerator, a thermal acid generator, a thermal base generator and amixture in any combination thereof; and wherein said monomer of formula(I) is having a refractive index of at least 1.5 and said composition isin a clear liquid form at room temperature.
 2. The composition accordingto claim 1, wherein said composition comprises first and second monomerof formula (I) distinct from each other and one of said first and secondmonomers having a refractive index of at least 1.5 and viscosity below100 centipoise, and wherein said first monomer is completely misciblewith said second monomer to form a clear solution.
 3. The compositionaccording to claim 1, wherein said composition forms a substantiallytransparent film when heated to a temperature from 50° C. to 100° C. 4.The composition according to claim 3, wherein said film has atransmission of equal to or higher than 90 percent of the visible light.5. The composition according to claim 3, wherein said film has atransmission of equal to or higher than 95 percent of the visible light.6. The composition according to claim 1, wherein the monomer of formula(I) is selected from the group consisting of:

5-(4-phenylbutyl)bicyclo[2.2.1]hept-2-ene;

5-(3-phenylpropyl)bicyclo[2.2.1]hept-2-ene;

5-phenethylbicyclo[2.2.1]hept-2-ene (PENB);

5-(benzyloxy)bicyclo[2.2.1]hept-2-ene;

5-octylbicyclo[2.2.1]hept-2-ene (OctNB);

5-decylbicyclo[2.2.1]hept-2-ene (DecNB);

4,4′-(bicyclo[2.2.1]hept-5-en-2-ylmethylene)bis(2,6-di-tert-butylphenol)(AOAONB);

bicyclo[2.2.1]hept-5-en-2-ylmethyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate (AONB);

5-norbornenylmethyleugenyl acetate (EuAcNB);

5-norbornenylmethyleugenol (EuOHNB);

(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)diphenylsilane(NBCH₂OSiMePh₂);

(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(ethyl)diphenylsilane;

(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(ethyl)(methyl)(phenyl)silane;

(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)dimethyl(phenyl)silane;

bicyclo[2.2.1]hept-5-en-2-yltrimethoxysilane (TMSNB);

bicyclo[2.2.1]hept-5-en-2-yltriethoxysilane (NBSKOC₂H₅)₃);

bicyclo[2.2.1]hept-5-en-2-yl(tert-butoxy)dimethoxysilane;

(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)trimethoxysilane;

NB(MeOH)₂; and

PhAcNB.
 7. The composition according to claim 1, wherein the latentcatalyst is an organo-ruthenium compound selected from the groupconsisting of a compound of formula (IIA), a compound of formula (IIB),a compound of formula (IIIA), a compound of formula (IIIB) and acompound of formula (IIIC):

and wherein: X is a halogen selected from the group consisting ofchlorine, bromine and iodine; Y is selected from the group consisting ofO and S; Y′ is OR₉SR₉ and —N═CHC(O)O(C₁-C₆)alkyl, where R₉ is selectedfrom the group consisting of methyl, ethyl, linear or branched(C₁-C₆)alkyl, (C₆-C₁₀)aryl, methoxy, ethoxy, linear or branched(C₁-C₆)alkoxy, (C₆-C₁₀)aryloxy, —OCH(CH₃)C(O)N(CH₃)(OCH₃); L is PR₃ orO═PR₃, where R is independently selected from the group consisting ofisopropyl, sec-butyl, tert-butyl, cyclohexyl, bicyclo(C₅-C₁₀)alkyl,phenyl, benzyl, isopropoxy, sec-butoxy, tert-butoxy, cyclohexyloxy,phenoxy and benzyloxy; R₇ is selected from the group consisting ofisopropyl, sec-butyl, tert-butyl, substituted or unsubstitutedcyclohexyl, substituted or unsubstituted phenyl, substituted orunsubstituted biphenyl and substituted or unsubstituted naphthyl; R₈ isselected from the group consisting of methyl, ethyl, linear or branched(C₁-C₆)alkyl, (C₆-C₁₀)aryl, methoxy, ethoxy, linear or branched(C₁-C₆)alkoxy, (C₆-C₁₀)aryloxy, —NHCO(C₁-C₆)alkyl,—NHCO-perfluoro(C₁-C₆)alkyl, —SO₂N((C₁-C₆)alkyl)₂ and —NO₂; Ar₁, Ar₂ Ar₃and Ar₄ are the same or different and each independently selected fromthe group consisting of substituted or unsubstituted phenyl, substitutedor unsubstituted biphenyl and substituted or unsubstituted naphthyl;wherein said substituents are selected from the group consisting ofmethyl, ethyl, iso-propyl, tert-butyl and phenyl.
 8. The compositionaccording to claim 7, wherein the organo-ruthenium compound is selectedfrom the group consisting of:

1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)(tricyclohexylphosphine)-(2-oxobenzylidene)ruthenium(VI)chloride;

where X=halogen, —OR_(a), —O(CO)R_(a)—OSO₂R_(a), where R_(a) is(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₄)aryl;

where X is Cl or I and R₁₀ is hydrogen, NO₂ or Cl;

cis-[1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-phenyl-1H-inden-1-ylidene)(triisopropylphosphite)ruthenium(II).9. The composition according to claim 1, wherein one or more additive isselected from the group consisting of:

methyl 4-(1-methyl)octahydropyrrolo[1,2-a]pyrimidine benzoate,commercially available as CGI 1293;

1-(1-phenylethyl)octahydropyrrolo[1,2-a]pyrimidine, commerciallyavailable as CGI 90;

and (4-thiophenyl)phenyl-diphenylsulfonium hexafluorophosphate;

bis-(triphenylsulfonium) sulfide bis-hexafluorophosphate (collectivelyTS-HFP);

tris(4-tert-butylphenyl)sulfonium perfluoro-1-butanesulfonate(TTBPS-PFBS);

tris(4-tert-butylphenyl)sulfonium triflate (TTBPS-TF);

triphenylsulfonium chloride (TSP-Cl);

(4-phenoxyphenyl)diphenylsulfonium triflate (PPDP-ST);

bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate (BTBI-PFBS);

bis(4-tert-butylphenyl)iodonium p-toluenesulfonate (BTBI-PTS);

bis(4-tert-butylphenyl)iodonium triflate (BTBPI-TF);

tolylcumyliodonium-tetrakis pentafluorophenylborate, commerciallyavailable as Rhodorsil 2074P;

diphenyliodonium chloride (DPI-Cl);

diphenyleneiodonium chloride (DPEI-Cl);

N-hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butanesulfonate(HNPCI-PFBS);

wherein R₁₁, R₁₂, R₁₃ and R₁₄ are the same or different and eachindependently selected from the group consisting of methyl, ethyl,linear or branched (C₃-C₁₆)alkyl, perfluoro(C₁-C₁₂)alkyl, substituted orunsubstituted (C₆-C₁₀)aryl, substituted or unsubstituted(C₆-C₁₀)aryl(C₃-C₁₆)alkyl, (C₃-C₁₂)cycloalkyl or wherein any two of R₁₁,R₁₂, R₁₃ and R₁₄ taken together with the nitrogen atom to which they areattached form a (C₃-C₁₂)cyclic or (C₅-C₁₂)bicyclic ring; and R₁₅ isselected from the group consisting of methyl, ethyl, linear or branched(C₃-C₁₆)alkyl, perfluoro(C₁-C₁₂)alkyl, substituted or unsubstituted(C₆-C₁₀)aryl and substituted or unsubstituted (C₆-C₁₀)aryl(C₃-C₁₆)alkyl;and

wherein n is an integer from 0 to 5; R₁₅ is as defined above; R₁₆selected from the group consisting of methyl, ethyl, linear or branched(C₃-C₁₆)alkyl, perfluoro(C₁-C₁₂)alkyl, substituted or unsubstituted(C₆-C₁₀)aryl and substituted or unsubstituted (C₆-C₁₀)aryl(C₃-C₁₆)alkyl;and R₁₇ is independently selected from the group consisting of methyl,ethyl, linear or branched (C₃-C₁₆)alkyl, perfluoro(C₁-C₁₂)alkyl,substituted or unsubstituted (C₆-C₁₀)aryl and substituted orunsubstituted (C₆-C₁₀)aryl(C₃-C₁₆)alkyl.
 10. A composition comprising:a) one or more monomers of formula (I):

wherein: m is an integer 0, 1 or 2; R₁, R₂, R₃ and R₄ are the same ordifferent and each independently selected from the group consisting ofhydrogen, halogen, methyl, ethyl, linear or branched (C₃-C₁₆)alkyl,perfluoro(C₁-C₁₂)alkyl, hydroxy(C₁-C₁₆)alkyl, (C₃-C₁₂)cycloalkyl,(C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl,(C₆-C₁₀)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₀)aryl,perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkyl, tri(C₁-C₆)alkoxysilyl and a group offormula (A):—Z-Aryl  (A) wherein: Z is a bond or a group selected from the groupconsisting of: (CR₅R₆)_(a), O(CR₅R₆)_(a), (CR₅R₆)_(a)O,(CR₅R₆)_(a)—O—(CR₅R₆)_(b), (CR₅R₆)_(a)—O—(SiR₅R₆)_(b),(CR₅R₆)_(a)—(CO)O—(CR₅R₆)_(b), (CR₅R₆)_(a)—O(CO)—(CR₅R₆)_(b),(CR₅R₆)_(a)—(CO)—(CR₅R₆)_(b), where a and b are integers which may bethe same or different and each independently is 1 to 12; R₅ and R₆ arethe same or different and each independently selected from the groupconsisting of hydrogen, methyl ethyl, linear or branched (C₃-C₆)alkyl,hydroxy, methoxy, ethoxy, linear or branched (C₃-C₆)alkyloxy, acetoxy,(C₂-C₆)acyl, hydroxymethyl, hydroxyethyl, linear or branchedhydroxy(C₃-C₆)alkyl, phenyl and phenoxy; Aryl is phenyl or phenylsubstituted with one or more of groups selected from the groupconsisting of methyl, ethyl, linear or branched (C₃-C₆)alkyl, hydroxy,methoxy, ethoxy, linear or branched (C₃-C₆)alkyloxy, acetoxy,(C₂-C₆)acyl, hydroxymethyl, hydroxyethyl, linear or branchedhydroxy(C₃-C₆)alkyl, phenyl and phenoxy; b) a latent organo-transitionmetal catalyst comprising a metal selected from the group consisting ofruthenium and osmium; and c) a dispersion comprising nanoparticles. 11.The composition according to claim 10, wherein said nanoparticlescomprised of at least one of hafnium oxide, zirconium oxide, titaniumoxide, hafnium-zirconium oxide, and titanium-zirconium oxide.
 12. Thecomposition according to claim 10, wherein the latent organo-transitionmetal catalyst is an organo-ruthenium compound selected from the groupconsisting of:

1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)(tricyclohexylphosphine)-(2-oxobenzylidene)ruthenium(VI)chloride;

where X=halogen, —OR_(a), —O(CO)R_(a)—OSO₂R_(a), where R_(a) is(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₄)aryl;

where X is Cl or I and R₁₀ is hydrogen, NO₂ or Cl;

cis-[1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-phenyl-1H-inden-1-ylidene)(triisopropylphosphite)ruthenium(II).13. The composition according to claim 10, which is comprised of5-norbomenylmethyl-eugenol,1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro-(phenylmethylidene)(tricyclohexylphosphine)rutheniumand zirconium oxide nanoparticles.
 14. A kit for forming a substantiallytransparent film comprising: a) one or more monomers of formula (I):

wherein: m is an integer 0, 1 or 2; R₁, R₂, R₃ and R₄ are the same ordifferent and each independently selected from the group consisting ofhydrogen, halogen, methyl, ethyl, linear or branched (C₃-C₁₆)alkyl,perfluoro(C₁-C₁₂)alkyl, hydroxy(C₁-C₁₆)alkyl, (C₃-C₁₂)cycloalkyl,(C₆-C₁₂)bicycloalkyl, (C₇-C_(1a))tricycloalkyl, (C₆-C₁₀)aryl,(C₆-C₁₀)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₀)aryl,perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkyl, tri(C₁-C₆)alkoxysilyl and a group offormula (A):—Z-Aryl  (A) wherein: Z is a bond or a group selected from the groupconsisting of: (CR₅R₆)_(a), O(CR₅R₆)_(a), (CR₅R₆)_(a)O,(CR₅R₆)_(a)—O—(CR₅R₆)_(b), (CR₅R₆)_(a)—O—(SiR₅R₆)_(b),(CR₅R₆)_(a)—(CO)O—(CR₅R₆)_(b), (CR₅R₆)_(a)—O(CO)—(CR₅R₆)_(b),(CR₅R₆)_(a)—(CO)—(CR₅R₆)_(b), where a and b are integers which may bethe same or different and each independently is 1 to 12; R₅ and R₆ arethe same or different and each independently selected from the groupconsisting of hydrogen, methyl ethyl, linear or branched (C₃-C₆)alkyl,hydroxy, methoxy, ethoxy, linear or branched (C₃-C₆)alkyloxy, acetoxy,(C₂-C₆)acyl, hydroxymethyl, hydroxyethyl, linear or branchedhydroxy(C₃-C₆)alkyl, phenyl and phenoxy; Aryl is phenyl or phenylsubstituted with one or more of groups selected from the groupconsisting of methyl, ethyl, linear or branched (C₃-C₆)alkyl, hydroxy,methoxy, ethoxy, linear or branched (C₃-C₆)alkyloxy, acetoxy,(C₂-C₆)acyl, hydroxymethyl, hydroxyethyl, linear or branchedhydroxy(C₃-C₆)alkyl, phenyl and phenoxy; b) a latent organo-transitionmetal catalyst comprising a metal selected from the group consisting ofruthenium and osmium; c) optionally one or more additives selected fromthe group consisting of a photoacid generator, a photobase generator, athermal acid generator, a thermal base generator and a mixture in anycombination thereof; and d) optionally a dispersion comprisingnanoparticles.
 15. The kit according to claim 14, which containsnanoparticles wherein said nanoparticles comprised of at least one ofhafnium oxide, zirconium oxide, hafnium-zirconium oxide andtitanium-zirconium oxide.
 16. The kit according to claim 14, whichcontains at least two monomers of formula (I) distinct from one another,wherein one monomer is completely soluble in the other monomer, and whensaid composition is heated to a temperature of from 50° C. to 100° C.for a sufficient length of time it forms a substantially transparentfilm having at least 90 percent of visible light transmission.
 17. Thekit according to claim 14, which contains5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), 5-norbornenylmethyl-eugenol,1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)(tricyclohexylphosphine)-(2-oxobenzylidene)ruthenium(VI)iodide and a mixture of (4-thiophenyl)phenyl-diphenylsulfoniumhexafluorophosphate and bis-(triphenylsulfonium) sulfidebis-hexafluorophosphate.
 18. The kit according to claim 14, whichcontains 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB),5-norbornenylmethyl-eugenol (EuOHNB) and zirconium oxide nanoparticles.19. A film comprising the composition of claim
 1. 20. A film comprisingthe composition of claim 10.